Hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate component,a group viii component and manganese or technetium,and process using said catalyst

ABSTRACT

A HYDROCRACKING CATALYST COMPRISING A LAYERED CLAYTYPE CRYSTALLINE ALUMINOSILICATE CRACKING COMPONENT, 0.01 TO 2.0 WEIGHT PERCENT, BASED ON SAID CRACKING COMPONENT AND CALCULATED AS THE METAL, OF A HYDROGENATING COMPONENT SELECTED FROM PLATINUM AND COMPOUNDS THEREOF, PALLADIUM AND COMPOUNDS THEREOF, AND IRIDIUM AND COMPOUNDS THEREOF, AND 0.01 TO 10.0 WEIGHTPERCENT, BASED ON SAID CRACKING COMPONENT AND CALCULATED AS THE METAL, OF A HYDROGENATING COMPONENT SELECTED FROM THE GROUP CONSISTING OF MANGANESE AND COMPOUNDS THEREOF AND TECHNETIUM AND COMPOUNDS THEREOF, AND PROCESSES USING SAID CATALYST.

s. M. cslcsER'Yf ET l- Jan. 26, '1971 HYDRO'ORAOKI sT` vCOMPRIS-ING AV LAYERED CLAY-.TYPE

slLlcATB COMPONENT, A GROUP l VIII 1 M,i4 AND NG OATALY CRYSTALLINE ALUMINO COMPONENT AND MANGANESE 0R TECHNETIU PROCESS USING SAID CATALYST Filed Maron 24, 1969.

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TORINEYS United States Patent Olhce 3,558,473 Patented Jan. 26, 1971 3,558,473 HYDROCRACKING CATALYST COMPRISING A LAYERED CLAY-TYPE CRYSTALLINE ALU- MINOSILICATE COMPONENT, A GROUP VIII COMPONENT AND MANGANESE OR TECHNE- TIUM, AND PROCESS USING SAID CATALYST Sigmund M. Csicsery, Lafayette, and James R. Kittrell,

El Cerrito, Calif., assignors to Chevron Research Company, San Francisco, Calif., a corporation of Delaware Filed Mar. 24, 1969, Ser. No. 809,617 The portion of the term of the patent subsequent to Oct. 20, 1987, has been disclaimed Int. Cl. C10g 37/02 U.S. Cl. 208-60 22 Claims ABSTRACT F THE DISCLOSURE INTRODUCTION This invention relates to catalytic hydrocracking of hydrocarbons, including petroleum distillates and solventdeasphalted residua, to produce high-value fuel products, including gasoline.

PRIOR ART It is well known that a wide variety of crystalline zeolitic molecular sieves may be used as the cracking component of hydrocracking catalysts. It is also well known that the preferred, and most commonly used, hydrogenating' components associated with these zeolitic cracking supports are platinum and palladium. Rabo et al. U.S. Pat. 3,236,761, for example, provides a particular type of decationized zeolitic molecular sieve catalyst, which may be used in some reactions without added metals, and in some reactions with added metals. The various appli-- cable reactions are isomerization, reforming, cracking, polymerization, al'kylation, dealkylation, hydrogenation, dehydrogenation and hydrocracking. Manganese is named as a metal with which the molecular sieve may be loaded, but it is not clear from the patent which reactions such a catalyst would be used to catalyze. No example of a manganese-molecular sieve catalyst is given, and the hydrocracking portion of the disclosure indicates that the molecular sieve catalyst of the patent may be used for hydrocraoking without added metals, but preferably with added platinum or palladium if a metal-loaded molecular sieve is to be used. Further, because of the great stress placed by the Rabo et al. patent on Group VIII metals in association with a molecular sieve cracking component, and particularly the noble metals, and the absence of any interest in manganese or other `Group VII metals except a passing mention, there is no guide in the patent either as to the applicability of a manganese-molecular sieve catalyst for the hydrocracking reaction in particular, or to the amount of manganese such a catalyst should contain, or as to the hydrocracking results that might be expected.

It is also known in the art that a catalyst may comprise manganese and palladium, both exchanged into a crystalline zeolitic molecular sieve. Mattox and Hammer U.S. Pat. 3,329,604 disclose such zeolitic catalysts wherein at least about 25% of the original alkali metal is replaced by manganese. Even with the highly effective ion exchange techniques used by them, this catalyst requires about 2.5% manganese to be effective and, judging from the examples, manganese levels in excess of 5% appear to be preferred. With the catalyst support used in the catalyst of the present invention, by contrast, a highly efficient and effective catalyst is obtained at much lower manganese levels, for example at levels of 0.5%. Indeed, high manganese concentrations surprisingly actually inhibit the action of the catalyst support material.

Manganese also has been disclosed as a component for non-zeolitic catalysts for many different hydrocarbon conversion processes. For example, Meyers et al. U.S. Pat. 2,848,510 suggests that 0.1 to 5% platinum or palladium in addition to 1 to 20% manganese oxide may be used on acid-activated clay, silica-alumina, and many other "reports, However, for a hydrocracking reaction, the acidactivated commercial clays are extremely ineffective with any level of the recited catalytic metals. Further, the layered, clay-type crystalline aluminosilicate of the catalyst of the present invention results in. higher catalytic activity and selectivity at low metal levels than any catalyst support comprehended by Meyers et al.

-It is also known from the art to use manganese together with a platinum group metal for stabilization of the platinum group metal to crystallite formation. For example, Meyers et al. U.S. Pat. 2,911,357 discloses a catalyst consisting of at least one metal from the group Pt, Pd and Rh with at least one metal from the group Co, Ru, Mn, Cu, Ag and Au. The use of the metals from the latter group inhibits the crystallization of metals from the former group, as indicated by X-ray measurements. For the hydrocracking reaction a catalyst consisting of Pt, Pd or Rh together with a metal from the group Co, :Ru, Cu, Ag and Au does not produce the superior results obtainable when Pt, Pd or Ir is used with Mn or Tc. Further, crystallization of Pd alone on the layered aluminosilicate of the catalyst of the present invention does not appear to occur during hydrocracking. The catalyst of the present invention produces results not obtainable with the catalysts disclosed in the above references.

It is also known that a crystalline zeolitic molecular sieve cracking component, while relatively insensitive to organic nitrogen compounds and ammonia, has a well ordered and uniform pore structure as a result of the crystal structure having bonds that are substantially equally strong in three dimensions. This provides definite limitations on the access of reactant molecules to the interiors of the pores.

It is also known, particularly from Granquist U.S. Pat. 3,252,757, that a relatively new layered crystalline alumino-silicate clay-type mineral that has been synthesized has the empirical formula nSiOZ A1203 :mAB :xH2O

where the layer lattices comprise said silica, said alumina, and said B, and where:

n is from 2.4 to 3.0

mis from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OH*, 1/20* and mixtures thereof, and s internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a dom spacing at said humidity Within the range which extends from a lower limit of about 10.4 A. to an upper limit of about 12.0 A.

when A is monovalent, to about 14.7 A. when A is divalent, and to a value intermediate between 12.0 A. and 14.7 A. when A. includes both monovalent and divalent cations. The equivalent of an exchangeable cation, A., in said catalyst may be chosen from the group consisting of H+, NH4+, Na+, Lit, K+, 1/2Ca+", 12Mg++, %Sr++, and 1/zBa-H', and mixtures thereof.

Said synthetic aluminosilicate mineral is a layered claytype crystalline aluminosilicate, which term as used herein is intended to include said synthetic mineral, similar synthetic minerals, and corresponding identical and similar natural minerals.

Said aluminosilicate mineral is known from U.S. Pat. 3,252,889 to have application in the dehydrated (calcined) form as a component of a, catalytic cracking catalyst; however, applications of said mineral as a component of a hydrocracking catalyst have not been disclosed heretofore, except in other patent applications of the assignee of the present application.

OBJECTS In view of the foregoing, objects of the present invention include providing a novel catalyst useful for hydrocracking, and a novel hydrocracking process using said catalyst, said catalyst:

1) Producing higher yields of gasoline, jet fuel or other liquid products and less butane and dry gas than are obtainable when operating with prior art catalysts at the same conditions and product cut point;

(2) Having a cost no greater than present commercial hydrocracking catalysts;

3) Having a cracking component less sensitive to nitrogen poisoning than silica-alumina gel;

(4) Having a cracking component that is crystalline in structure, having pores elongated in two directions, contrary to the pores of crystalline zeolitic molecular sieves, and therefore having less reactant access limitations than the pores of such molecular sieves;

(5) Having a rst hydrogenating component providing increased activity and stability to said catalyst, compared with a similar catalyst not containing said component;

(6) Having a second hydrogenating component providing additional activity and stability so said catalyst, compared with the same catalyst which contains said irst hydrogenating component but not said second hydrogenating component;

(7) Having a high hydrocracking activity with economically low levels of the hydrogenating components.

It is a further object of the present invention to provide various embodiments of a hydrocracking process using a catalyst having the aforesaid characteristics, including methods of further improving catalyst stability, and methods of operating the hydrocracking process in an integrated manner with other process units to achieve various advantageous results.

The present invention will best be understood, and further objects and advantages thereof will be apparent, from the following description when read in connection with the accompanying drawing.

DRAWING In the drawing, FIG. l is a diagrammatic illustration of apparatus and flow paths suitable for carrying out the process of several of the embodiments of the present invention, including embodiments wherein a hydrolining zone precedes the hydrocracking zone, and embodiments wherein a selected fraction from the hydrocracking zone is catalytically reformed;

FIG. 2 is a diagrammatic illustration of apparatus and flow paths suitable for carrying out the process of additional embodiments of the present invention, including embodiments wherein a hydroning zone precedes a hydrocracking zone in a single reactor shell, and embodiments wherein a selected fraction from the hydrocracking zone is catalytically cracked.

STATEMENT OF INVENTION It has been found that a catalyst comprising a layered clay-type crystalline aluminosilicate cracking component, for example the layered synthetic clay-type crystalline aluminosilicate mineral of Granquist U.S. Pat. 3,252,757, a hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof, in an amount of 0.01 to 2.0 weight percent, calculated as metal and based on said cracking component, and a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, in an amount of 0.01 to 10.0 weight percent, calculated as metal and based on said cracking component, has all of the desirable catalyst attributes listed under Objects above and, therefore, in accordance with the present invention there is provided such a catalyst and a hydrocracking process using such a catalyst. It is not obvious from Rabo et al. U.S. Pat. 3,236,761 that a manganese-crystalline zeolitic molecular sieve catalyst has application as a hydrocracking catalyst or what manganese levels such a catalyst should contain. It is even less obvious from Rabo et al. or from Mattox et al. U.S. Pat. 3,329,604 that not only should manganese be used as a component of a hydrocracking catalyst, but that the layered synthetic crystalline aluminosilicate mineral of Granquist U.S. Pat. 3,252,757 should be used instead of a crystalline zeolitic molecular sieve. Even if such matters were clear from Rabo et al. or Mattox et al., Meyers et al. U.S. Pat. 2,848,510 would lead a man skilled in the art to conclude that such a catalyst would need to contain considerably more than 2 weight percent manganese. It has been found that this conclusion is not correct. Accordingly, it has been found that the catalyst of the present invention surprisingly provides advantages over the Rabo et al. platinum or palladium on molecular sieve hydrocracking catalyst and the Meyers palladium-manganese-silica-alumina hydrocracking catalyst, while unexpectedly being free from disadvantages that the art would lead one to expect. In particular, in the catalyst of the present invention: (l) the presence of the component selected from managanese and compounds thereof and technetium and compounds thereof results in a catalyst of higher activity and stability than a catalyst that is identical except that contains no manganese or technetium; and (2) the presence of the component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof results in a catalyst of higher activity and stability than a catalyst that is identical except that contains no such Group VIII component; (3) the specic combination of the Group VII component and the Group VIII component provides enhanced activity and stability while at the same time producing exceptionally high yields of liquid products; and (4) the unusually low metals level results in no signicantly detrimental effects on catalyst performance.

In accordance with the present invention, therefore, there is provided a hydrocracking catalyst comprising a layered, clay-type crystalline aluminosilicate cracking component, 0.01 to 2.0 weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof, and 0.01 to 10.0 weight percent, preferably 0.01 to 2.0 weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, said cracking component having, prior to drying and calcining of said catalyst, the empirical formula IzSiOZ: A1203 mAB :.rHgO

where the layer lattices comprise said silica, said alumina, and said B, and where:

n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of Fr, OH, V20- and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a dom spacing at said humidity within the range which extends from a lower limit of about 10.4 Angstroms to an upper limit of about 12.0 Angstroms when A is monovalent, to about 14.7 Angstroms when A is divalent, and to a valve intermediate between 12.00 Angstroms and 14.7 Angstroms when A includes both monovalent and divalent cations.

Further in accordance with the present invention there is provided a catalyst effective for various hydrocarbon conversion reactions, including hydrocracking, hydrodesulfurization, hydrodenitrification, hydrogenation and hydroisomerization, comprising:

(A) A layer-type, crystalline clay-like mineral cracking component having, prior to drying and calcining said catalyst, the empirical formula nSiO2: A1203 mAB :xH2O

where the layer lattices comprise said silica, said alumina, and said B, and where:

n is from 2.4 to 3.0

m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, OHj 1/20-w and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a 1001 spacing at said humidity within the range which extends from a lower limit of about 10.4 A. to an upper limit of about 12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, and to a value intermediate between 12.0 A. and 14.7 A. when A includes both monovalent and divalent cations, and

(B) A hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof, in an amount of 0.01 to 2.0 weight percent, based on said cracking component and calculated as metal, and a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, in an amount of 0.01 to 10.0 weight percent, based on said cracking component and calculated as metal.

Said cracking component may be present in said catalyst in an amount of to 99.9 weight percent, based on the total catalyst. If desired, said catalyst may further comprise a crystalline zeolitic molecular sieve cracking component in the amount of l to 50 weight percent, based on the total catalyst. The equivalent of an exchangeable cation, A, in said catalyst may be chosen from the group consisting of H+, NHU, Na+, Lit', K+, 1/2Ca++, 1/2Mg++, 1/zSr++, and 1/2Ba++, and mixtures thereof.

Said catalyst additionally may comprise a component selected from the group consisting of alumina and silicaalumina and a hydrogenating component selected from the group consisting of Group VI metals and compounds thereof and nickel and compounds thereof. When the catalyst comprises alumina or silica-alumina, titania advantageously may be present also. When the catalyst comprises nickel or a compound thereof, tin or a compound thereof advantageously may be present also. When said catalyst comprises said additional components, preferably the catalyst is prepared by coprecipitation of all noncrystalline components to form a slurry, followed by addition of the layered clay-type crystalline aluminosilicate component (and additionally a crystalline zeolitic molecular sieve component, if desired) to the slurry in particulate form, followed by filtering, washing and drying to produce a hydrogel matrix having said crystalline component (or components) dispersed therethrough. Preferably the finished catalyst will have substantially all of the catalytic metal or metals located in the matrix, and said crystalline component (or components) will be substantially in the ammonia or hydrogen form, and will be substantially free of catalytic loading metal or metals; that is, said crystalline component: (or components) will contain less than about 0.5 weight percent of catalytic metal or metals. This result will obtain if addition of said crystalline component (or components) to the slurry of other catalyst components is accomplished at a pH of 5 or above.

Further in accordance with the present invention, there is provided a hydrocracking process which comprises contacting a hydrocarbon feedstock containing substantial amounts of materials boiling above 200 F. and selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates, in a reaction zone with hydrogen and the aforesaid catalyst comprising a layered clay-type crystalline aluminosilicate at hydrocracking conditions including a temperature in the range 400 to 950 F., a pressure in the range 800 to 3,500 p.s.i.g., a liquid hourly space velocity in the range 0.1 to 5.0, and a total hydrogen supply rate of 200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, and recovering from said reaction zone valuable products, including gasoline. The hydrogen feedstock preferably contains less than 1,000 p.p.m. organic nitrogen. A prior hydroning step may be used, if desired, to reduce the feed nitrogen content to the preferred level; however, because of the superior nitrogen tolerance of the layered clay-type crystalline alumimosilicate component, compared with silica-alumina, the hydroning step need not accomplish complete nitrogen content reduction, as further discussed hereinafter.

Further in accordanxce with the present invention, advantageous results are obtained by providing in the reaction zone, in addition to said catalyst comprising a layered clay-type crystalline aluminosilicate, a separate second catalyst comprising a hydrogenating component selected from Group VI metals and compounds thereof, a hydrogenating component selected from `Group VIII metals and compounds thereof, and a component selected from the group consisting of alumina and silica-alumina. Further in accordance with the present invention, said separate second catalyst may be located in'said reaction zone in a bed disposed above said catalyst comprising a layered clay-type crystalline aluminosilicate cracking component. In the embodiments of the present invention discussed in this paragraph, no other prior hydroning step generally will be necessary, because hydrol'ining is accomplished in one reaction zone concurrently with hydrocracking, together with some hydrogenation of aromatics.

Still further in accordance with the present invention, there is provided a hydrocracking process which comprises sequentially contacting a hydrocarbon feedstock and hydrogen with a rst bed of catalyst and then with a second bed of catalyst, said catalyst beds both being located within a single elongated reactor pressure shell, said first bed of catalyst being located in an upper portion of said shell, the catalyst of `said first bed comprising a hydrogenating component selected4 from the group consisting of Group VI metals and compounds thereof and Group VIII metals and compounds thereof, and a component selected from the group consisting of alumina and silica-alumina, the catalyst of said second bed being said catalyst comprising a layered clay-type crystalline aluminosilicate, maintaining said first bed of catalyst and said second bed of catalyst at a temperature in the range 400 to 950 F. and a pressure in the range 800 to 3,500 p.s.i.g. during said contacting, maintaining the total supply rate of said hydrogen into said reactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, and recovering a gasoline product from the effluent of said second bed of catalyst.

The hydrocracking zone of the process of the present invention may be operated once through, or advantageously may be operated by recycling thereto materials from the effluent thereof that boil above 200 F., preferably above 400 F. All or a portion of these heavier materials advantageously may be catalytically cracked. The heavy gasoline fraction from the hydrocracking zone advantageously may be catalytically reformed.

HYDROCARBON FEEDSTOCKS The feedstocks supplied to the hydrocracking zone containing said catalyst comprising a layered clay-type crystalline aluminosilicate in the process of the present invention are selected from the group consisting of petroleum distillates, solvent-deasphalted petroleum residua, shale oils and coal tar distillates. The feedstocks contain substantial amounts of materials boiling above 200 F., preferably substantial amounts of materials boiling in the range 350 to 950 F., and more preferably in the range 400 to 900 F. Suitable feedstocks include those heavy distillates normally defined as heavy straight-run gas oils and heavy cracked cycle oils, as Well as conventional FCC feed and portions thereof. Cracked stocks may be obtained from thermal or catalytic cracking of various stocks, including those obtained from petroleum, gilsonite, shale and coal tar. As discussed hereinafter, the feedstocks may have been subjected to a hydrolining and/or hydrogenation treatment, which may have been accompanied by some hydrocracking, before being supplied to the hydrocracking zone containing said catalyst comprising a layered clay-type crystalline aluminosilicate.

NITROGEN CONTENT OF FEEDSTOCKS While the process of the present invention can be practiced with utility when supplying to the hydrocracking zone containing a catalyst comprising a layered clay-type crystalline aluminosilicate, hydrocarbon feeds containing relatively large quantities of organic nitrogen, for example several thousand parts per million organic nitrogen, it is preferred that the organic nitrogen content be less than 1,000 parts per million organic nitrogen. A preferred range is 0.05 to 1,000 parts per million; more preferably, 0.05 to 100 parts per million. As previously discussed, a prior hydroining step may be used, if desired, to reduce the feed nitrogen content to the preferred level. The prior hydrofining step advantageously may also accomplish hydrogenation and a reasonable amount of hydrocracking. Because of the superior tolerance of the layered clay-type crystalline aluminosilicate component for organic nitrogen compounds, compared with silicaalumina, the hydrofining step need not accomplish complete organic nitrogen content reduction. Further, because of the superior tolerance of said component for ammonia, compared with silica-alumina, and because said component is more tolerant of ammonia than of organic nitrogen compounds, ammonia produced in the hydroning zone either may be removed from the system between the hydroiining zone and the hydrocracking zone containing the hydrocracking catalyst comprising said component, or may be permitted to pass into the hydrocracking zone along with the feed thereto.

SULFUR CONTENT OF FEEDSTOCK While the process of the present invention can be practiced with utility when supplying to the hydrocracking zone, containing a catalyst comprising a layered clay-type crystalline aluminosilicate, hydrocarbon feeds containing relatively large quantities of organic sulfur, it is preferable to maintain the organic sulfur content of the feed to that zone in a range of 0 to 3 Weight percent, preferably Oto 1 weight percent.

Catalyst comprising a layered clay-type crystalline aluminosilicate component, a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, and a hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof (A) General.-The layered clay-type crystalline aluminosilicate used in preparing the catalyst may be any catalytically active layered clay-type aluminosilicate, although the synthetic mineral described above and in Granquist U.S. Pat. 3,252,757 is preferred. This component will be present in the catalyst in an amount of 10 to 99.9 Weight percent, based on the total catalyst. The mineral becomes dehydrated when the catalyst is dried and calcined as in the examples herein.

The Group VII hydrogenating component of the catalyst may be present in the final catalyst in the form of the metal, metal oxide, metal sulfide, or a combination thereof. The manganese or compound thereof or technetium or compound thereof may be combined with the layered clay-type crystalline aluminosilicate cracking component, or may be combined with other catalyst components in which said cracking component is dispersed, or both. In any case, the manganese or technetium will be present in an amount of 0.01 to 10.0 Weight percent, based on said cracking component and calculated as the metal.

When a conventional crystalline zeolitic molecular sieve cracking component is included in the catalyst, said molecular sieve cracking component may be of any type that is known in the art as a useful component of a conventional hydrocracking catalyst comprising a noble metal-compound hydrogenating component. A decationized molecular sieve cracking component is preferred. Especially suitable are faujasite, particularly Y type and X type faujasite, and mordenite, in the ammonia form, hydrogen form, alkaline earth-exchanged form, or rare earth-exchanged form.

The hydrogenating component of the catalyst that is selected from platinum, palladium, iridium, and cornpounds of platinum, palladium and iridium may be present in the final catalyst in the form of the metal, metal oxide, metal sulfide, or a combination thereof. This component may be combined with the layered clay-type crystalline aluminosilicate cracking component, or may be combined with other catalyst components in which said aluminosilicate cracking component is dispersed, or both. In any case, the component will be present in an amount of 0.01 to 2.0 Weight percent, based on said aluminosilicate cracking component and calculated as the metal.

A preferred catalyst comprises a layered clay-type crystalline aluminosilicate cracking component intimately dispersed in a matrix of other catalytic components cornprising alumina, silica-alumina, or silica-alumina-titania. The manganese or Vcompound thereof or technetium or compound thereof and the platinum, palladium or iridium, or compound of platinum, palladium or iridium may be combined with said aluminosilicate cracking component before the latter is dispersed in the matrix, or the manganese or compound thereof or technetium or compound thereof and the platinum, palladium or iridium, or compound of platinum, palladium or iridium may be a portion of the matrix. Examples of suitable matrices, in addition to matrices consisting of alumina or silica-alumina, include matrices comprising: (a) palladium or a cornpound thereof and technetium or manganese or a compound thereof and silica-alumina; (b) palladium or a compound thereof and technetium or manganese or a compound thereof and alumina; (c) iridium or a compound thereof and technetium or manganese or a compound thereof and alumina; (d) iridium or a compound thereof and technetium or manganese or a compound thereof and silica-alumina; (e) platinum or a compound thereof and technetium or manganese or a compound thereof and alumina; (f) platinum or a compound thereof and technetium or manganese or a compound thereof and silica-alumina; (g) any of the foregoing with the addition of nickel or a compound thereof or nickel or a compound thereof plus tin or a compound thereof; if desired, the nickel or compound thereof may be accompanied by a Group VI metal or compound thereof.

(B) Method of preparation-The layered clay-type crystalline aluminosilicate cracking component of the catalyst may be prepared in the manner set forth in Granquist U.S. Pat. 3,252,757.

In the case wherein manganese or a compound thereof or technetium or a compound thereof and platinum, palladium or iridium, or compound of platinum, palladium or iridium are added directly to the layered clay-type crystalline aluminosilicate cracking component, impregnation using aqueous solutions of suitable hydrogenating metal compounds or adsorption of suitable hydrogenating metal compounds are operable methods of incorporating the hydrogenating component or compounds thereof into said aluminosilicate component. Ion exchange methods whereby the hydrogenating components are incorporated into said aluminosilicate component by exchanging those components with a metal component already present in said aluminosilicate component may be used. However, in such methods it is preferred to use compounds wherein the metals to be introduced into said aluminosilicate component are present as cations.`

In the case wherein said aluminosilicate cracking component first is dispersed in a matrix of other catalytic components and manganese or a compound thereof or technetium or a compound thereof and platinum, palladium or iridium, or a compound of platinum, palladium or iridium are introduced into the resulting composition, impregnation using an aqueous solution of suitable hydrogenating component compounds or adsorption of suitable hydrogenating component compounds are the preferred methods.

The manganese or technetium compound used in the impregnation or adsorption step may be any convenient compound, for example chloride or nitrate.

The platinum, palladium or iridium compound used in preparing the catalyst may be any convenient compound, for example platinum, palladium or iridium chloride, tetra `ammino palladium nitrate, etc.

Where the layered clay-type crystalline aluminosilicate component, with or without added hydrogenating components, is dispersed in a matrix of other catalyst components, the dispersion may be accomplished by cogelation of said other components around said aluminosilicate component in a conventional manner.

Following combination of the catalyst components, the resulting composition may be washed free of impurities and dried at a temperature in the range 500 to 1200 F., preferably 900 to 1l50 F., for a reasonable time, for example 0.5 to 48 hours, preferably 0.5 to 20 hours.

The finished catalyst may be suliided in a conventional manner prior to use, if desired. If not presulfided, the catalyst may tend to become suliided during process operation from any sulfur compounds that may be present in the hydrocarbon feed. As discussed elsewhere herein, the equilibrium degree of sultiding at a given operating ternperature will be different than in a corresponding catalytic system Wherein a noble metal component alone is present, with no manganese or technetium being present.

Separate hydrolining catalyst (A) General.-As previously indicated, advantageous results are obtained by providing in the reaction zone containing the hydrocracking catalyst of the present invention a separate second catalyst comprising a hydrogenating component selected from Group VI metals and compounds thereof, a hydrogenating component selected from Group VIII metals and compounds thereof, and a support selected from the group consisting of alumina and silica-alumina. Pellets or other particles of this separate second catalyst may be physically mixed with said hydrocracking catalyst, but preferably are disposed in a separate catalyst bed located ahead of said hydrocracking catalyst in the same reactor shell, eliminating interstage condensation, pressure letdown and ammonia and hydrogen sulfide removal. In a preferred arrangement using downflow of hydrocarbon feed, the bed of separate second catalyst is located above said .hydrocracking catalyst in the same reactor shell.`

Where said separate second catalyst is located in theV same reactor shell as the hydrocracking catalyst of the present invention, it is preferably present in an amount in the range of l0 to 40 volume percent of the total amount of catalyst in the reactor.

In an arrangement preferred to the ones discussed above in this section, the separate second catalyst may be located in a separate hydroning reactor, operated under conventional hydrofining conditions, from the effluent of which ammonia or hydrogen sulfide, or both, and also hydrocarbon products, if desired, may be removed prior to hydrocracking the remaining hydroiined feedstock in a subsequent hydrocracking reactor in the presence of the catalyst of the present invention.

In any of the arrangements discussed in this section, the separate second catalyst preferably has hydroiining activity and hydrogenation activity', and even more preferably also has enough hydrocracking activity to convert 0.2 to 50, preferably 5 to 20, weight percent of the hydrocarbon feedstock to products boiling below the initial boiling point of the feedstock in a single pass. The hydrogenation activity preferably is sufficient to saturate or partially saturate a substantial portion of the organic oxygen, nitrogen and sulfur compounds in the feed to water, ammonia and hydrogen sulfide.

Preferably, said separate second catalyst contains nickel or cobalt or compounds thereof in an amount of l to 15 weight percent, calculated as metal, and molybdenum or tungsten or compounds thereof, in an amount of 5 to 30 weight percent, calculated as metal, with the remainder of the catalyst consisting of alumina, or silicaalumina containing up to 50 weight percent silica.

Particularly preferred examples of said separate second catalyst, comprising silica-alumina, are:

Percent by weight of total catalyst,

calculated as metal SiO2/A1203, N1 M0 W Weight ratio 4-10 15-25 10/90 to 30/70. 6-15 15-30 30/70 to 50/50.

It has been found that use of said separate second catalyst increases the gasoline yield from the hydrocracking stage containing the catalyst of the present invention, compared with the gasoline yield from the hydrocracking stage 'when the identical feed thereto has not been first or concurrently processed in the presence of said separate second catalyst, The increased gasoline yield probably is related to the hydro genation, in that more saturated hydrocarbon structures tend to crack more easily.

(B) Method of preparation-Said separate second catalyst may be prepared by any conventional preparation method, including impregnation of an alumina or silicaallumina support with salts of the desired hydrogenating component, or cogelation of all components, with the latter method being preferred.

It has been found that use of said separate second catalyst in the above-described arrangements further increases the stability of the hydroeracking catalyst of the present invention, compared with the stability of the latter 1 1 catalyst when the identical feed thereto has not Ibeen irst or concurrently processed in the presence of said separate second catalyst.

OPERATING yCONDITIONS The hydrocracking zone containing the catalyst of the present invention is operated at hydrocracking conditions including a temperature in the range 400 to 950 F., preferably 500 to 850 F., a pressure in the range 800 to 3,500 p.s.i.g., preferably 1,000 to 3,000 p.s.i.g., a liquid hourly space velocity in the range 0.1 to 5.0, preferably 0.5 to 5.0, and more preferably `0.5 to 3.0. The total hydrogen supply rate (makeup and recycle hydrogen) to said zone is 200 to 20,000 s.c.f., preferably 2,000 to 20,000 s.c.f., of hydrogen per barrel of said feedstock.

Where a separate hydroiining zone, which also may accomplish hydrogenation and some hydrocracking, is located ahead of the hydrocracking zone containing the catalyst of the present invention, the operating conditions in the separate hydroiining zone include a temperature of 400 to 900 F., preferably 500 to 800 F., a pressure of 800 to 3500 p.s.i.g., preferably 1000 to 2500 p.s.i.g., and a liquid hourly space velocity of 0.1 to 5.0, preferably 0.5 to 3.0. The total hydrogen supply rate (makeup and recycle hydrogen) is 200 to 20,000 s.c.f. of hydrogen per barrel of feedstock, preferably 2,000 to 20,000 s.c.f, of hydrogen per barrel of feedstock.

Where a separate bed of hydroning catalyst is located above a bed of the hydrocracking catalyst of the present invention in the same reactor shell, the space velocity through the bed of hydroning catalyst will be a function of the space velocity through the hydrocracking catalyst bed and the amount of hydrofining catalyst expressed as a volume percent of the total catalyst in the reactor. For example, where the hydrofining catalyst is 25 volume percent of the total catalyst in the reactor, and the space velocity through the lbed of hydrocracking catalyst is 0.9, -the space velocity through the bed of hydroning catalyst will be 2.7. Accordingly, the space velocity through the bed of hydrolining catalyst in the process of the present invention may range from 0.15 to 45.0.

The operating conditions in the reforming zone and catalytic cracking zone employed in various embodiments of the present invention are conventional conditions known in the art.

PROCESS OPERATION WITH REFERENCE TO DRAWING Referring now to FIG. 1 of the drawing, in accordance with a primary embodiment of the present invention, a hydrocarbon feedstock as previously described, which in this case may boil above 400 F., is passed through line 1 into hydrocracking zone 2, which contains a hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate cracking component, 0.01 to 2.0 Weight percent, |based on said cracking component, of platinum, palladium or iridium, and 0.01 to 10.0 Weight percent, based on said cracking component, of manganese or technetium. As previously discussed, said layered aluminosilicate component may be dispersed in a matrix of other catalyst components, vvhich matrix may contain all or a portion of the hydrogenating components. Also as previously discussed, a separate second catalyst, previously described, may be located in hydrocracking zone 2. The feedstock is hydrocracked in hydrocracking zone 2 at conditions previously discussed, in the presence of hydrogen supplied through line 3. From hydrocracking zone 2 an efuent is Withdrawn through line 4, hydrogen is separated therefrom in separator 5, and hydrogen is recycled to hydrocracking zone 2 through line 6. From separator 5, hydrocracked materials `are passed through lines 7 and 8 to distillation column 9, where they are separated into fractions, including a C4- fraction which is withdrawn through line 10, a C5--l80 F. fraction which 12 is withdrawn through line 11, and a l-400 F. fraction Which is withdrawn through line 12.

Still referring to FIG. l, in accordance With another embodiment of the present inveniton, the -400 F. fraction in line 12 is reformed under conventional catalytic reforming conditions in reforming zone 13, from which a catalytic reformate is Withdrawn through line 14.

Still referring to FIG. l, in accordance with another embodiment of the present invention, the 180-400 F. stock which is to be hydroiined and/or hydrogenated, and partially hydrocracked, if desired, in a separate hydrotreating zone prior to being hydrocracked in hydrocracking zone 2, is passed through line 15 to hydrotreating zone 116 containing a catalyst, as previously described, having hydroning and/ or hydrogenation activity. The feedstock is hydrotreated in zone 16 at conditions previously described, in the presence of hydrogen supplied through line 17. The efuent from hydrotreating zone 16 is passed through line 18 to separation zone 19, from which hydrogen separated from the treated feedstock is recycled through line 20 to hydrotreating zone 16. In zone y19, fwater entering through line 21 is used to scrub ammonia and other contaminants from the incoming hydrocarbon stream, and the ammonia, Water and lother contaminants are Withdraw from zone 19 through line 22. The scrubbed feedstock is passed through line 8 to distillation column 9 `and thence to hydrocracking zone 2.

Referring now to FIG. 2, a hydrocarbon feedstock, as previously described, which in this case may boil above 400 F., is passed through line 29 to hydrotreating zone 30 containing a catalyst, as previously described having hydrofining and/or hydrogenation activity. The feedstock is hydroned and/or hydrogenated, and partially hydrocracked, if desired, in zone 30, at conditions previously described, in the presence of hydrogen supplied through line 31. The eflluent from zone 30 is passed through line 32, without intervening impurity removal, yinto hydrocracking zone 33, Where it is hydrocracked in the presence of a hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate cracking component and 0.01 to 2.0 weight percent, based on said cracking component, of platinum, palladium or iridium, and 0.01 to 10.0 Weight percent, based on said cracking component, of manganese or technetium, Said catalyst may contain other catalytic components, and a separate second catalyst may be present in zone 33, as described in connection with zone 2 in FIG. 1. Hydrotreating zone 30 and hydrocracking zone 33 may be located in separate reactor shells, which may be operated at different pressures. Alternatively, and in a preferred manner of operation, hydrotreating zone 30 and hydrocracking zone 33 may be separate catalyst beds located in -a single pressure shell 34, and the effluent from zone 30 may be passed to zone 33 without intervening pressure letdown, condensation or impurity removal. The effluent from zone 33 is passed through line 35 to separation zone 36, from which hydrogen is recycled through line 37 to hydrotreating zone 30. All or a portion of the recycled hydrogen may be passed through line 38 to hydrocracking,

zone 33, if desired. In separation zone 36, water entering through line 40 is used to scrub ammonia and other contaminants from the incoming hydrocarbon stream, and the ammonia, Water and other contaminants are withdrawn from zone. 36 through line 41. The eluent from zone 36 is passed through line 42 to distillation column 43, where it is separated into fractions, including a C4- fraction which is withdrawn through line 44, a C5-180o F. fraction which is withdrawn through line 45, a 180- 400 F.+ fraction which is withdrawn through line 46, and a fraction boiling above 400 F. which is withdrawn through line 47. The fraction in line 47 may be recycled through lines 48 and 49 to hydrocracking zone 33. All 0r a portion of the fraction in line 48 may be recycled to hydrotreating zone 30 through line 50, if desired.

Still referring to FIG. 2, in accordance with another embodiment of the present invention, the 180-400 F, fraction in line 46 may be passed to a catalytic reforming zone S, where it may be reformed in the presence of a conventional catalytic reforming catalyst under conventional catalytic reforming conditions to produce a catalytic reformate, which is withdrawn from zone 55 through line 56.

Still referring to FIG. 2, in another embodiment of the present invention, all or a portion of the fraction in line 47 may be passed through line 57 to catalytic cracking zone 58, which may contain a conventional catalytic cracking catalyst and which may be operated under conventional catalytic cracking conditions, and from which a catalytically cracked eluent may be withdrawn through line 59.

EXAMPLES The following examples are given for the purpose of further illustrating the practice of the process of the present invention. However, it is to be understood that these examples are not intended in any way to limit the scope of the present invention.

Example 1 A catalyst consisting of manganese and a layered claytype crystalline aluminosilicate (Catalyst A, a comparison catalyst) is prepared in the following m-anner.

These starting materials are used:

(l) 500 grams of a layered synthetic crystalline aluminosilicate mineral as described in Granquist U.S. Pat. 3,252,757;

(2) 1,000 cc. of an aqueous solution of manganese nitrate, Mn(NO3)2, containing 2.5 grams of manganese.

The mineral, in lumpy powder form, is introduced into a Hobart kitchen blender, followed by slow addition of the manganese nitrate solution while stirring, to form a pasty mass. The pasty mass is transferred to a dish and dried at 150 F. for approximately 16 hours. The resulting dried material is crushed and calcined in flowing air for 2 hours at 950 F.

Example 2 A layered aluminosilicate-palladium catalyst (Catalyst B, a comparison catalyst) was prepared in the following manner. v

These starting materials were used:

(1) 500 grams of a layered clay-type aluminosilicate in finely divided Afor-m.

(2) 6.8 grams of tetra ammino palladium nitrate [Pd(NH3)4] (NO3)2, dissolved in 700 ml. of H2O.

The layered aluminosilicate in powder form was mixed with the tetra ammino palladium nitrate solution, to form a pasty mass. The pasty mass was dried in a vacuum oven for 6 hours at room temperature, then at 200-250 F. for approximately 16 hours. The resulting material was tabletted, and then calcined in flowing dry air for 4 hours at 460 F., then for 4 hours at 900 F. The resulting catalyst upon analysis was found to contain 0.5 weight precent palladium, calculated as metal.

Example 3 A layered aluminosilicate-palladium-manganese catalyst (Catalylst C, a catalyst according to the present invention) was prepared in the following manner.

These starting materials were used:

(1) 500 grams of a layered clay-type aluminosilicate in nely divided form.

(2) 6.6 grams of tetra ammino palladium nitrate [Pd(NH3)4](NO3)2, and 15.8 grams of a stock solution containing 51.4% Mn(NO3)2 dissolved in 1,235 ml. of H2O.

The layered alurninosilicate in powder form was mixed with the tetra ammino palladium nitrate-manganese nitrate solution, to form a pasty rnass. The pasty mass was dried in a vacuum oven for 6- hours at room temperature, then at 200-250 F. for approximately 16 hours. The resulting material was tabletted, and then calcined in Gravity, API 30.1 Aniline point, F 132 Sulfur content, p.p.m. 5

Nitrogen content, ppm. ASTM D-1160 distillatioin ST/S 409/446 10/30 460/486 50 523 The hydrocracking was acomplished, on a recycle liquid basis, at a pressure of 1,200 p.s.i.g., a liquid hourly space velocity of 1.5, a per-pass conversion of 60 liquid volume percent below 400 F., and a hydrogen supply rate of approximately 7,000 s.c.f./bbl. The same test is performed with the catalyst of Example 1. The following results are obtained:

Catalyst A B C Starting temperature, F 600 490 500 Fouling rate, F./hr 0. 06 O. 11 0. 02 05+ liquid yield, wt. percent 91. 5 90 91. 5 Temperature after 1,000 hrs., F 666 000 520 Of these catalysts, Catalyst C is the superior catalyst, because it has a much lower fouling rate that Catalysts A and B, a higher initial activity than Catalyst A, and

`an initial activityVclose to that of Catalyst B. After only 1,000 hours operation, Catalyst C is more active than Catalyst B, more active than Catalyst A, and has a lower fouling rate than either. Furthermore, use of Catalyst C results in a significantly higher C5+ gasoline yield than Catalyst B.

l Example 5 The 180400 F. portion of the product of Example 4, resulting from use of Catalyst C, is catalytically reformed, using a conventional reforming catalyst and conventional reforming conditions, and is found to be a superior feedstock for this operation. The catalytic reformate is combined with the C5-180 F. portion of the product of Example 4, to produce a gasoline pool.

Example 6 The 400 F.+ portion of the product of Example 4, resulting from use of Catalyst C, is recycled to the catalytic cracking unit which produced the light cycle oil feed used in Example 4. This upgrades the total feed to the catalytic cracking unit, and causes decreased coke production and increased gasoline production in that unit. These improved results are made possible because of the improved characteristics of the 400 F.+ materials recycled from the hydrocracking zone to the catalytic cracking unit, compared with the approximately 400 F.+ light cycle oil supplied to the hydrocracking zone from the catalytic cracking unit.

Example 7 A catalyst prepared exactly as in Example 3, and having the same composition as Catalyst C of Example 3, is used to hydrocrack another portion of the same light cycle oil hydrocarbon feedstock that is referred to in Example 4. The hydrocracking is accomplished on a one-through basis, that is, with the 400 F.+ portion of the product not being recycled to the hydrocracking zone.

Example 8 The 180-400 F. portion of the product of Example 7 is catalytically reformed, using a conventional reforming catalyst and conventional reforming conditions, and is found to be a superior feedstock for this operation. The catalytic reformate is combined with the C-180 F. portion of the product of Example 7, to produce a gasoline pool.

Example 9 A rst bed of hydrocracking catalyst prepared exactly as in Example 3, and having the same composition as Catalyst C of Example 3, is placed in a reactor. A second bed of catalyst is placed in the reactor above the first bed. The volume of the second bed is 25% of the total catalyst volume. The catalyst in the second bed, prepared by impregnation of metals on silica-alumina pellets, has the following composition:

Weight percent NiO 7.6 M003 27.0 S102 14.4 A1203 51.0

Another portion of the same light cycle oil feedstock that is referred to in Example 4 is passed downwardly through both catalyst beds in the reactor together with added hydrogen, the hydrogen and cycle oil sequentially contacting the catalyst beds, with no product or impurity removal between beds.

Example The 180-400 F. portion of the product of Example 9 is catalytically reformed, using a conventional reforming catalyst and conventional reforming conditions, and is found to be a superior feedstock for this operation. The catalytic reformate is combined with the C5-180 F. portion of the product of Example 9 to produce a gasoline pool.

CONCLUSIONS Applicants do not intend to be bound by any theory for the unexpected superior activity and stability of the catalysts of the present invention. However, they assume that the favorable results are largely attributable to: (1) a different, and more favorable, equilibrium at a given operating temperature for the system consisting of manganese or technetium metal, the various manganese or technetium oxides, the various manganese or technetium suldes, platinum, palladium or iridium metal, the various oxides of platinum, palladium or iridium, the various suliides of platinum, palladium or iridium, and sulfur and hydrogen, than for the system consisting of platinum metal, platinum oxide, platinum sulfide, sulfur and hydrogen, which provides a hydrocracking catalyst superior to the Rabo et al. noble-metal-containing catalyst; and (2) an interaction between the effect of manganese or technetium or components of manganese or technetium and a layered clay-type crystalline aluminosilicate cracking component that produces more favorable hydrocracking results than are produced by any interaction between the effect of manganese or a manganese cornpound and a gel-type silica-alumina cracking component such as is used in the Meyers catalyst.

It has been shown that the process of the present invention has advantages over conventional hydrocracking processes, particularly in that the hydrocracking catalyst comprising a layered clay-type crystalline aluminosilicate cracking component, a manganese or manganese-compound or technetium or technetium-compound hydrogenating component, and a hydrogenating component selected from platinum, palladium and iridium and compounds of platinum, palladium and iridium, is nitrogentolerant and sulfur-tolerant, has a high stability, and has high cracking activity.

Although only specific embodiments of the present invention have been described, numerous variations can be made in these embodiments without departing from the spirit of the invention, and all such variations that fall within the scope of the appended claims are intended to be embraced thereby.

What is claimed is:

1. A hydrocracking catalyst comprising a layered claytype aluminosilicate cracking component, 0.01 to 2.0 Weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from platinum and compounds thereof, palladium and compounds thereof, and iridium and compounds thereof, and 0.01 to 10.0 weight percent, based on said cracking component and calculated as the metal, of a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, said cracking component having, prior to drying and calcining of said catalyst, the empirical formula nSi02 A1203 mAB xHZO where the layer lattices comprise said silica, said alumina, and said B, and where nis from 2.4 to 3.0 m is from 0.2 to 0.6

A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice,

B is chosen from the group of negative ions which consists of F, 0H, 1/20 and mixtures thereof, and is internal in the lattice, and

x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a dom spacing at said humidity within the range which extends from a lower limit of about 10.4 Angstroms to an upper limit of about 12.0 Angstroms when A is monovalent, to about 14.7 Angstroms when A is divalent, and to a value intermediate between 12.0 Angstroms and 14.7 Angstroms when A includes both monovalent and divalent cations.

2. A catalyst as in claim 1, which further comprises a matrix containing a component selected from alumina gel and silica-alumina gel.

3. A catalyst as in claim 2, which further comprises at least one hydrogenating component selected from Group VI metals and compounds thereof and nickel and compounds thereof.

4. A catalyst as in claim 2, wherein said layered claytype crystalline aluminosilicate cracking component is in particulate form, and is dispersed through said matrix.

5. A catalyst as in claim 2, which further comprises titania.

6. A catalyst as in claim 4, wherein said layered claytype crystalline aluminosilicate cracking component is substantially in the ammonia or hydrogen form and is su'bstantially free of any catalytic metal or metals, and wherein said hydrogenating components are contained in said matrix.

7. A catalyst as in claim 6, which further comprises titania.

8. A catalyst as in claim 6, which further comprises tin or a compound of tin.

9. A catalyst comprising:

(A) a layer-type, crystalline, clay-type cracking component having, before drying and calcining of said catalyst, the empirical formula A1203 I :XHZO

where the layer lattices comprise said silica, said alumina, and said B, and where n is from 2.4 to 3.0 m is from 0.2 to 0.6 A is one equivalent of an exchangeable cation having a valence not greater than 2, and is external to the lattice, B is chosen from the group of negative ions which 17 consists of F, OH, 1/20 and mixtures thereof, and is internal in the lattrice, and x is from 2.0 to 3.5 at 50% relative humidity,

said mineral being characterized by a dom spacing at said humidity within the range which extends from a lower limit of about 10.4 A. to an upper limit of about 12.0 A. when A is monovalent, to about 14.7 A. when A is divalent, and to a valve intermediate betweenl 12.0 A. and 14.7 A; when A includes both monovalent and divalent cations, and

(B) a hydrogenating component selected from platinum and compounds therefof, and palladium and compounds thereof, and iridium and compounds thereof, in an amount of 0.01 to 2.0 weight percent, based on said cracking component and calculated as metal, and a hydrogenating component selected from manganese and compounds thereof and technetium and compounds thereof, in an amount of 0.01 to 10.0 weight percent, based on said cracking component and calculated as metal.

10. A catalyst as in claim 9, wherein said mineral is present in an amount of to 99.9 weight percent, based on the total catalyst.

11. A catalyst as in claim 9, which further comprises a crystalline zeolitic molecular sieve component, in the amount of 1 to 50 weight percent, based on the total catalyst.

12. A catalyst as in claim 9, wherein A is chosen from the group consisting of H+,4 `NH4+, Na+, Li+, K+, 1/zCa++, 1/zMgJflZ 1/2Srl+, and l/zBa+ and mixtures thereof.

13. A hydrocracking process which comprises contacting a hydrocarbon feedstock containing substantial amounts of materials boiling above 200 F. and selected from the group consisting of petroleum distillates, solventdeasphalted petroleum residua, shale oils and coal tar distllates, in a reaction zone with hydrogen and the catalyst of claim 1, at hydrocracking conditions including a temperature in the range 400 to 950 F., a pressure in the range 800 to 3,500 p.s.i.g., a liquid hourly space velocity in the range 0.1 to 5.0 and a total hydrogen supply rate of 200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, and recovering from said reaction zone valu able products, including gasoline.

14. A process as in claim 13, wherein said catalyst further comprises a component selected from the group consisting of alumina gel and silica-alumina gel.

15. A process as in claimk14, wherein said catalyst further comprises at least one hydrogenating component selected from the group consisting of Group VI metals and compounds thereof and nickel and compounds thereof.

16. A process as in claim 13, wherein said hydrocarbon feedstock contains 0.05 to 1,000 p.p.m. organic nitrogen.

17. A process as in claim 13, wherein said reaction zone contains, in addition to said catalyst, a separate second catalyst comprising a hydrogenating component selected from Group VI metals and compounds thereof, a hydrogenating component selected from Group VIII metals and compounds thereof, and a component selected from the group consisting of alumina and silica-alumina.

18. A process as in claim 17, wherein said separate second catalyst is located in said reaction zone in a bed disposed above said catalyst comprising a layered claytype crystalline alumino-silicate cracking component.

19. A hydrocracking process which comprises sequentially contacting a hydrocarbon feedstock and hydrogen with a first bed of catalyst and then with a second bed of catalyst, said catalyst beds both being located within a single elongated reactor pressure shell, said first lbed of catalyst being located in an upper portion of said shell, the catalyst of said first bed comprising a hydrogenating component selected from the group consisting of Group VI metals and compounds thereof and Group VIH metals and compounds thereof and a component selected from the group consisting of alumina and silica-alumina, the catalyst of said second bed being the catalyst of claim 1, maintaining said first bed of catalyst and said second bed of catalyst at a temperature in the range 400 to 950 F. and a pressure in the range 800 to 3,500 p.s.i.g. during said contacting, maintaining the total supply rate of said hydrogen into said reactor shell from 200 to 20,000 s.c.f. of hydrogen per barrel of said feedstock, and recovering a gasoline product from the eluent of said second bed of catalyst.

20. A process as in claim 19, wherein the eiiiuent from said secondbed of catalyst is separated into fractions, including a light gasoline fraction, a heavy gasoline fraction, and a fraction boiling generally higher than said heavy gasoline fraction.

21. A process as in claim 20, wherein said heavy gasoline fraction is catalytically reformed.

22. A process as in claim 20, wherein said fraction boiling generally higher than said heavy gasoline fraction is catalytically cracked.

References Cited `UNITED STATES PATENTS 3,132,087 5/1964 Kelley et al 208--60 3,140,253 7/1964 Plank et al 208-120 3,236,761 2/1966 Rabo et al 208-111 3,252,757 5/1966 Granquist 208-120 DELBERT E. GANTZ, Primary Examiner A. RIMENS, Assistant Examiner U.S. C1. X.R..

20S-59, lll, 120; 252-455 mg? UNITED STATES PATENT OFFICE CERTIFICATE OF CGRRECTION Patent No. 3,558 ,1473 Dated January 26 l973.

1nventor(s) SIGMUND M. CSICSERY et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Col. 3, line 3 "when A. includes" should read --when A includes.

Col. 8 lines 38-39 "comprising a noble metal-compound hydrogenatng component." should read --comprising a noble metal or noble metal-compound hydrogenating component..

Col. 12, lines 9-10 "the 180l4001". stock" should read --a hydrocarbon feedstock.

Signed and sealed this 1 7th day of August 1 971 (SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JE Attesting Officer' Commissioner of Patent: 

